TWI506134B - Polymers for laundry detergents - Google Patents

Description

Polymer for laundry detergent

The present invention is generally directed to improved detergent compositions comprising acrylic polymers.

Polymers prepared from acrylic acid are known as additives to laundry detergents. For example, U.S. Patent No. 5,409,629 discloses a polymer comprising polymerized residues of acrylic acid and ethyl acrylate. However, this prior art does not disclose a polymer which is given as an excellent result of a laundry detergent additive according to the present invention.

The problem addressed by the present invention is to provide an improved detergent composition comprising an acrylic polymer.

The present invention relates to a detergent composition comprising: (a) from 8 to 50 wt% of a surfactant; and (b) from 0.05 to 4 wt% of at least one polymer comprising the following polymerized residues: (i) 40 to 80 wt% of a C ₁ -C ₄ alkyl acrylate; wherein the C ₁ -C ₄ alkyl acrylate is at least 4/10 ethyl acrylate; (ii) 20 to 52 wt% C ₃ -C ₆ a carboxylic acid monomer; and (iii) from 0 to 10% by weight of a monomer having an alkyl group having at least 10 carbon atoms.

All percentages are by weight (wt%), all parts by weight, and all temperatures are °C, unless otherwise specifically indicated. Measurements made at "room temperature" are measurements made at 20 °C to 25 °C. As is known in the art, the weight average molecular weight ( _Mw ) is measured on a hydrolyzed polymer by gel permeation chromatography (GPC) using a polyacrylic acid standard. The GPC technique is discussed in detail in Modern Size Exclusion Chromatography, WW Yau, JJ Kirkland, DD Bly; Wiley-Interscience, 1979 and A Guide to Materials Characterization and Chemical Analysis, JP Sibilia; VCH, 1988, p. 81-84. The molecular weights reported herein are in units of Daltons. As used herein, "(meth)acrylic" means acrylic or methacrylic. The "C ₃ -C ₆ carboxylic acid monomer" is a monoethylenically unsaturated compound having one or two carboxylic acid groups such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride. , Crotonic acid, etc. The alkyl group is a saturated hydrocarbon group which may be a straight chain or a branched chain. The aralkyl group is an alkyl group substituted with an aryl group. Examples of the aralkyl group include, for example, a benzyl group, a 2-phenylethyl group, and a 1-phenylethyl group. The aralkylphenyl group is a phenyl group having one or more aralkyl substituents such as 2,4,6-gin(1-phenylethyl)phenyl.

Preferably, the polymer-based acrylic polymer, i.e., has at least 50 wt%, preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt%, preferably at least 98 wt% The polymerized residue of the acrylic monomer. The acrylic single system comprises (meth)acrylic acid and its C ₁ -C ₂₂ alkyl ester or hydroxyalkyl ester, including the structure H ₂ C=C(R)CO ₂ (CH ₂ CH ₂ O) _n (CH(R' ) CH ₂ O) _m R"monomer; crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, (meth) acrylamide, (meth) acrylonitrile and crotonic acid, An acid or fumaric acid or a hydroxyalkyl ester of maleic acid. The acrylic polymer may also comprise other polymerized monomer residues including, for example, nonionic (meth) acrylates, cationic singles. Body, H ₂ C=C(R)C ₆ H ₄ C(CH ₃ ) ₂ NHCO ₂ (CH ₂ CH ₂ O) _n (CH(R')CH ₂ O) _m R", H ₂ C=C( R)C(O)X(CH ₂ CH ₂ O) _n (CH(R')CH ₂ O) _m R", monounsaturated dicarboxylic acid esters, vinyl esters, vinyl decyl amines (including For example, N-vinylpyrrolidone), a sulfonated acrylic monomer, a vinyl sulfonic acid, an ethylene halide, a phosphorus-containing monomer, a heterocyclic monomer, styrene, and substituted styrene. Preferably, The polymer contains no more than 5% by weight, preferably no more than 3% by weight, preferably no more than 2% by weight, preferably no more than 1% by weight of sulfur- or phosphorus-containing monomer. Preferably, the polymerization Having from 10,000 to 220,000, preferably from 10,000 to 190,000, preferably from 15,000 to 170,000, preferably from 20,000 to 100,000, preferably in the range of from 20,000 to 60,000 of weight average molecular weight (M _w).

Preferably, the detergent composition comprises from 35 to 85 wt% water. Preferably, the detergent composition comprises at least 40 wt%, preferably at least 45 wt%, preferably at least 50 wt%, preferably at least 60 wt% water. Preferably, the detergent composition comprises no more than 70 wt%, preferably no more than 60 wt%, preferably no more than 50 wt%, preferably no more than 45 wt%, preferably no more than 40 wt% water . Preferably, the detergent composition is a liquid or gel at 20 °C.

Preferably, the surfactant comprises at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant. Preferably, the nonionic surfactant has an alkyl group having at least 10 carbon atoms and at least 5 polymerized ethylene oxide or propylene oxide residues. Preferably, the anionic surfactant has an alkyl group having at least 10 carbon atoms and preferably an anion group selected from the group consisting of a sulfonate and a caboxylate. The anionic surfactant also has a polymeric residue of ethylene oxide and/or may have an aromatic ring, such as a linear alkylbenzene sulfonate. Certain anionic surfactants are fatty acid alkali metal salts. Preferably, the detergent composition comprises at least 20 wt%, preferably at least 25 wt%, preferably at least 30 wt%, preferably at least 35 wt%, preferably at least 40 wt% of a surfactant. Preferably, the detergent composition comprises no more than 46% by weight, preferably no more than 42% by weight, preferably no more than 38% by weight, and preferably no more than 34% by weight of surfactant. Preferably, the detergent composition comprises at least 6 wt%, preferably at least 8 wt%, preferably at least 10 wt%, preferably at least 12 wt%, preferably at least 14 wt% linear alkylbenzene sulfonate. Preferably, the detergent composition comprises no more than 20% by weight, preferably no more than 18% by weight, and preferably no more than 16% by weight of linear alkylbenzene sulfonate.

The detergent composition contains from 0.05 to 4 wt% of at least one polymer calculated on the basis of the polymer solids relative to the overall weight of the detergent. Preferably, the detergent composition comprises at least 0.2 wt%, preferably at least 0.3 wt%, preferably at least 0.4 wt%, preferably at least 0.5 wt%, preferably at least 0.6 wt%, preferably at least 0.8 wt%. The polymer. Preferably, the detergent composition contains no more than 3.5% by weight, preferably no more than 3% by weight, preferably no more than 2.5% by weight, preferably no more than 2% by weight, and preferably no more than 1.5% by weight of polymer. . If more than one polymer is present, the total amount of such polymers is within the limits of the above disclosure. The detergent composition may also contain from 5 to 30% by weight, preferably from 8 to 20% by weight of other components, such as solvents (eg, propylene glycol, ethanol; typically 4 to 8 wt%), fragrances, enzymes, rheology Modifiers, salts (eg, sodium citrate), sodium (potassium) carbonate/potassium and/or (b) sodium citrate/potassium and other chelating agents such as methylglycine-N,N-diacetic acid (MGDA) , glutamic acid-N,N-diacetic acid (GLDA), 2-hydroxyethyliminodiacetic acid (HEIDA), or a salt thereof such as a sodium salt.

Preferably, the polymer comprises at least 42 wt%, preferably at least 44 wt%, preferably at least 46 wt%, preferably at least 48 wt%, preferably at least 50 wt%, preferably at least 52 wt%, It is preferably at least 55 wt%, preferably at least 60 wt% of a polymerized residue of a C ₁ -C ₄ alkyl acrylate. Preferably, the polymer comprises no more than 78 wt%, preferably no more than 76 wt%, preferably no more than 74 wt%, preferably no more than 72 wt%, preferably no more than 70 wt%, preferably no more than 68 a polymerized residue of wt% of a C ₁ -C ₄ alkyl acrylate. Preferably, the C ₁ -C ₄ alkyl acrylate residue is a C ₂ -C ₃ alkyl acrylate residue, preferably ethyl acrylate (EA). Preferably, the C ₁ -C ₄ alkyl acrylate is at least 5/10 by weight, preferably at least 6/10 by weight, preferably at least 7/10 by weight, preferably at least 8/10 by weight, preferably at least 9/10. The weight is ethyl acrylate; preferably, the remainder of the C ₁ -C ₄ alkyl acrylate is n-butyl acrylate (BA) and/or methyl acrylate (MA). Preferably, the polymer system contains no more than 15 wt%, preferably not more than 10 wt%, preferably not more than 7 wt%, preferably not more than than 4 wt% of acrylic acid C ₁ -C ₄ alkyl esters of ( A polymeric residue of a methyl acrylate.

Preferably, the polymer comprises at least 22 wt%, preferably at least 24 wt%, preferably at least 26 wt%, preferably at least 28 wt%, preferably at least 30 wt%, preferably at least 32 wt% C A polymerized residue of a _{3- C6} carboxylic acid monomer. Preferably, the polymer comprises a polymerization of no more than 50 wt%, preferably no more than 48 wt%, preferably no more than 45 wt%, preferably no more than 40 wt% of a C ₃ -C ₆ carboxylic acid monomer. Residues. Preferably, the C ₃ -C ₆ carboxylic acid monosystem C ₃ -C ₄ carboxylic acid monomer; preferably (meth)acrylic acid, preferably methacrylic acid (MAA). Preferably, the polymer comprises no more than 30 wt%, preferably no more than 28 wt%, preferably no more than 26 wt% of the polymerized residue of acrylic acid (AA).

Preferably, when the polymer comprises at least 50% by weight of a polymerized residue of a C ₁ -C ₄ alkyl acrylate, the polymer also comprises at least 8 wt% of AA polymerized residues, preferably at least 10 wt. The polymerized residue of % AA, preferably at least 12 wt% of the polymerized residue of AA, preferably at least 15 wt% of the polymerized residue of AA. Preferably, when the polymer system comprises at least 55 wt% of acrylic polymerized residues of C ₁ -C ₄ alkyl ester group, the polymer also comprises at least 10 wt% polymerized residues of AA, preferably at least 12 wt The polymerized residue of % AA, preferably at least 15% by weight of the polymerized residue of AA, preferably at least 20% by weight of the polymerized residue of AA. Preferably, when the polymer comprises at least 50% by weight of a polymerized residue of a C ₁ -C ₄ alkyl acrylate, at least 7/10 (preferably at least 8/10) of which is EA, the polymer also comprises At least 8 wt% of AA polymerized residue, preferably at least 10 wt% of AA polymerized residue, preferably at least 12 wt% of AA polymerized residue, preferably at least 15 wt% of AA polymerized residue.

Preferably, when the polymer contains from 40 to 60% by weight (preferably from 42 to 55 wt%) of a polymerized residue of a C ₁ -C ₄ alkyl acrylate, the polymer also contains no more than 28 wt% The polymerized residue of AA, preferably not more than 25% by weight of AA polymerized residue, preferably not more than 22% by weight of AA polymerized residue, preferably not more than 19% by weight of AA polymerized residue, Preferably no more than 15 wt% of AA polymerized residues.

Preferably, the polymer contains no more than 8 wt%, preferably no more than 6 wt%, preferably no more than 3 wt%, preferably no more than 1 wt% of an alkyl group having at least 10 carbon atoms. Polymeric residue of the monomer. Preferably, the polymer contains no more than 7 wt%, preferably no more than 5 wt%, preferably no more than 3 wt%, preferably no more than 1 wt% of an alkyl group having at least 8 carbon atoms. Polymeric residues of a monomer having an alkyl group of at least 6 carbon atoms, preferably an alkyl group having at least 4 carbon atoms, are preferred. Examples of such monomers are alkyl (meth)acrylates and monomers of the following structure: H ₂ C=C(R)C(O)X(CH ₂ CH ₂ O) _n (CH(R')CH ₂ O) _m R" or H ₂ C=C(R)C ₆ H ₄ C(CH ₃ ) ₂ NHCO ₂ (CH ₂ CH ₂ O) _n (CH(R')CH ₂ O) _m R"; X is O or NH, R is H or CH ₃ , R' is C ₁ -C ₂ alkyl; R" is C ₈ -C ₂₂ alkyl, C ₈ -C ₁₆ alkylphenyl or C ₁₃ -C ₃₆ aralkylphenyl; n is the average number of 6 to 100, m is the average number of 0 to 50, provided that n ≧ m and m + n are from 6 to 100. Preferred (meth)acrylic acid C ₁₀ -C _{a 22} -alkyl ester of a C ₁₀ -C ₁₈ alkyl (meth)acrylate, preferably a C ₁₂ -C ₁₈ alkyl (meth)acrylate. Typically, having the structure H ₂ C=C(R)C(O) X(CH ₂ CH ₂ O) _n (CH(R')CH ₂ O) _m R" of the monomer, X is O; R" is a C ₈ -C ₂₂ alkyl group, or a C ₁₀ -C ₂₂ alkane a group, or a C ₁₂ -C ₂₀ alkyl group; n is 15 to 30, and m is 0 to 5; further, n is 18 to 25 and m is 0 to 3; further, n is 18 to 25 and m is 0 to 2; and R' and R are methyl groups. Preferably, the polymer contains no more than 10% by weight, preferably no more than 7% by weight, preferably no more than 5% by weight, preferably no more than 2% by weight. Not a monomer of an acrylic monomer Polymerized residues.

The polymer may be a crosslinked polymer, that is, a copolymer component and a crosslinking agent, such as a monomer having two or more non-conjugated ethylenically unsaturated groups, during the polymerization. Preferred examples of such monomers include, for example, diallyl ethers or triallyl ethers of diols or polyols, and bis(meth) propylene phthalate or tris(meth) propylene oxime esters (e.g., Trimethylolpropane diallyl ether, ethylene glycol dimethacrylate), diallyl or triallyl ester of diacid or triacid, allyl (meth)acrylate, divinyl fluorene , triallyl phosphate, divinyl aromatic (eg, divinylbenzene). Preferably, the amount of the polymeric crosslinker residue in the polymer is no more than 0.3 wt%, preferably no more than 0.2 wt%, preferably no more than 0.1 wt%, preferably no more than 0.05 wt%, preferably Not more than 0.02 wt%, preferably not more than 0.01 wt%.

Preferably, the polymer acts as an aqueous composition comprising a polymer as discrete particles dispersed in an aqueous medium. In the aqueous dispersion, the average particle diameter of the polymer particles is typically in the range of 20 to 1,000 nanometers (nm), preferably in the range of 50 to 500 nm, more preferably in the range of 75 to 350 nm. Herein, the particle size is reported as "effective diameter" as measured by a Brookhaven BI-90 particle size measuring instrument manufactured by Brookhaven Instruments Corporation (Holtsville, NY). In the aqueous dispersion, the concentration of the polymer particles is typically in the range of 15 to 60% by weight, preferably 20 to 50% by weight based on the weight of the aqueous dispersion.

Preferably, the pH of the liquid laundry detergent composition is adjusted to from 7 to 11, preferably from 8 to 10, preferably from 8 to 9.5. Suitable bases for adjusting the pH of the formulation include inorganic bases such as sodium hydroxide and potassium hydroxide; ammonium hydroxide; and organic bases such as mono-, di- or triethanolamine. Mixtures of bases can also be used. Suitable acid groups for adjusting the pH of the formulation include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; and organic acids such as acetic acid. Mixtures of acids can also be used.

Suitable polymerization techniques for use in the process of the present invention include emulsion polymerization and solution polymerization, preferably emulsion polymerization. The aqueous emulsion polymerization process is typically carried out in an aqueous reaction mixture containing at least one monomer and a plurality of synthetic adjuvants such as a free radical source, a buffer, and a reducing agent in an aqueous reaction medium. Preferably, a chain transfer agent is used to limit the molecular weight, and the chain transfer agent is preferably a mercaptan, preferably a C8-C12 alkyl mercaptan. The aqueous reaction medium is a continuous fluid phase of the aqueous reaction mixture and contains more than 50% by weight water, based on the weight of the aqueous reaction medium, and optionally one or more water miscible solvents. Suitable solvents which are miscible with water include methanol, ethanol, propanol, acetone, ethylene glycol ethyl ether, propylene glycol propyl ether, and diacetone alcohol. Preferably, the aqueous reaction medium contains more than 90% by weight water, more preferably more than 95% by weight water, based on the weight of the aqueous reaction medium. Most preferably, the aqueous reaction medium contains from 98 to 100% by weight, based on the weight of the aqueous reaction medium, of water.

[Examples]

The acrylic single system described herein includes acrylic acid (AA), methacrylic acid (MAA), ethyl acrylate (EA), n-butyl acrylate (BA), methyl acrylate (MA), lauryl methacrylate. (LMA), MA-23 (methacrylate of 23 moles of decyl alcohol ethoxylate). N-dodecyl mercaptan (nDDM) is commonly used as a chain transfer agent. The amount of each monomer is calculated as a percentage of the total amount of monomers (excluding nDDM), and the amount of nDDM is also given as a percentage of total monomers, that is, excluding nDDM, the sum of monomer percentages. Is 100.

Witco 90 Flake = anionic sodium dodecyl benzene sulfonate (linear alkyl benzene sulfonate), 90% active; NEODOL 25-7 alcohol ethoxylate = average about 7 moles per mole of alcohol A nonionic C12-C15 alcohol of ethylene oxide in the ear, 100% active.

WITCOLATE LES-60C = anionic C12-C14 (3 moles EO) sodium sulfate, 60% active.

EMPICOL ESB 70 = anionic C12-C14 (2 molar EO) sodium sulfate, 70% active;

ACUSOL 820 = Hydrophobically modified alkali soluble acrylic polymer emulsion (HASE), which is immediately thickened when neutralized to a pH greater than 7 by the addition of a base; PRIFAC 7908 from Croda Coatings & Polymers.

Formulation for anti-redeposition test

A 10.5% surfactant formulation for anti-redeposition laundry testing.

The final pH of the formulation was adjusted to 8.8

26.0% surfactant formulation for anti-redeposition laundry testing.

The final pH of the formulation was adjusted to 8.8

37.4% surfactant/soap formulation for anti-redeposition laundry testing.

The final pH of the formulation was adjusted to 8.5

A 35.6% surfactant/soap formulation with a rheology modifier for the anti-redeposition laundry test.

Anti-redeposition laundry results

Experiment 571

Starting laundry conditions:

The total volume of water is 1 liter (L). Add 1.0 g (3) of 37.4% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca ⁺² /Mg ⁺² ), US testing company Tergotometer, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4 cm (cm) cotton Two pieces of 8.9 x 11.4 cm PE/cotton, two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (Cotton-Interlock) (all from Test Fabrics). At the beginning of each wash, add 2.5g of Dust Sebum Emulsion (scientific services) and 2.5g of 25% Big Oak Clay slurry (large oak clay) An orange-colored, high-iron clay found locally in Pennsylvania. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

A total of 16 cycles of whiteness index - WIE 313 (average of 4 values from Hunter Lab Colorimeter):

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw, 5,800 Mn; I: 50% EA/50% MAA with 3.0% nDDM, 24,506 Mw, 4,450 Mn; J: 65% EA/35% MAA, with 3.0% nDDM, 22,897 Mw, 4,124 Mn; K-28.3% EA/28.3% BA/43.3% MAA with 3.0% nDDM, 21,929 Mw, 4,001 Mn; Comp.AA: 100% AA, 7,500 Mw, 2,297 Mn (comparative example).

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 574

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; E: 28.3% EA/28.3% BA/43.3% MAA with 1.25% nDDM, 54,472 Mw; F: 50% EA/50% MAA, With 1.5% nDDM, 51,080 Mw.

G: 65% EA/35% MAA with 1.3% nDDM, 56, 101 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 575

Starting laundry conditions: The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (4 averages from the value of the Hunter Lab Colorimeter):

Sample composition:

B: 28.3% EA/28.3% BA/43.3% MAA with 2% nDDM, 35,152 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA, With 2% nDDM, 31,771 Mw.

H: 40% EA/50% MAA/10% LMA with 2% nDDM, 103,790 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 576

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

I: 50% EA/50% MAA with 3.0% nDDM, 24,506 Mw; J: 65% EA/35% MAA with 3.0% nDDM, 22,897 Mw; Comp. A: 80% AA/20% EA, 21,000 Mw (Comparative example).

Comp. B: 90% AA/10% EA, 18,929 Mw (comparative example).

Experiment 577

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; I-50% EA/50% MAA with 3.0% nDDM, 24,506 Mw; J: 65% EA/35% MAA with 3.0% nDDM , 22,897 Mw; K: 28.3% EA/28.3% BA/43.3% MAA with 3.0% nDDM, 21,929 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 578

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

B: 28.3% EA/28.3% BA/43.3% MAA with 2% nDDM, 35,152 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA, With 2% nDDM, 31,771 Mw.

H: 40% EA/50% MAA/10% LMA with 2% nDDM, 103,790 Mw.

Experiment 579

Formulation stability test with 10.0% surfactant formulation with 1% polymer solids. The final formulation pH was 8.5.

10% surfactant preparation for formulation stability testing.

The pH of the formulation was adjusted to 8.5 with 10% NaOH.

Note: The initial observations showed that the above 16 samples were clear and stable in yellow.

Stability data after 2 weeks under the conditions disclosed in the table

Stability: A single clear phase was observed with no precipitation or unevenness

Phase separation: A second liquid layer was observed at the bottom of the vessel indicating some phase incompatibility between the components.

Stability data after 4 weeks under the conditions disclosed in the table

Stability: A single clear phase was observed with no precipitation or unevenness

Phase separation: A second liquid layer was observed at the bottom of the vessel indicating some phase incompatibility between the components.

NTU: Turbidity turbidity unit measured on a DRt Model 100 HF instrument (HF Instruments Model DRt 100).

Sample index:

B: 28.3% EA/28.3% BA/43.3% MAA with 2% nDDM, 35,152 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA, With 2% nDDM, 31,771 Mw; E: 28.3% EA/28.3% BA/43.3% MAA with 1.25% nDDM, 54,472 Mw; F: 50% EA/50% MAA with 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA with 1.3% nDDM, 56,101 Mw.

H: 40% EA/50% MAA/10% LMA with 2% nDDM, 103,790 Mw; I: 50% EA/50% MAA with 3.0% nDDM, 24,506 Mw; J: 65% EA/35% MAA, With 3.0% nDDM, 22,897 Mw.

K: 28.3% EA/28.3% BA/43.3% MAA with 3% nDDM, 21,929 Mw; Comp. A: 80% AA/20% EA, 21,000 Mw; Comp. B: 90% AA/10% EA, 18, 929 Mw;Comp. C: 80% AA/20% EA, 25,372 Mw; Comp. D: 90% AA/10% EA, 27,935 Mw.

Experiment 580

Formulation stability test of 24.7% surfactant preparation with 1% polymer solids. The final formulation pH was 8.5.

Note: The initial observations show that sample 1 and samples 3 through 12 are pale yellow clarified and stable. Sample 2 was initially cloudy but became clear within 24 hours. Samples 13 to 16 were slightly turbid.

24.7% surfactant preparation for formulation stability testing.

The pH of the formulation was adjusted to 8.5 with 10% NaOH.

Stability data after 2 weeks under the conditions disclosed in the table

Stability: A single clear phase was observed with no precipitation or unevenness

Phase separation: A second liquid layer was observed at the bottom of the vessel indicating some phase incompatibility between the components.

Stability data after 4 weeks under the conditions disclosed in the table

Stability: A single clear phase was observed with no precipitation or unevenness

Phase separation: A second liquid layer was observed at the bottom of the vessel indicating some phase incompatibility between the components. N/A: Not applicable

Sample index:

B: 28.3% EA/28.3% BA/43.3% MAA with 2% nDDM, 35,152 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA, With 2% nDDM, 31,771 Mw; E: 28.3% EA/28.3% BA/43.3% MAA with 1.25% nDDM, 54,472 Mw; F: 50% EA/50% MAA with 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA with 1.3% nDDM, 56,101 Mw; H: 40% EA/50% MAA/10% LMA with 2% nDDM, 103,790 Mw; I: 50% EA/50% MAA with 3.0 % nDDM, 24,506 Mw; J: 65% EA/35% MAA with 3.0% nDDM, 22,897 Mw.

K: 28.3% EA/28.3% BA/43.3% MAA with 3% nDDM, 21,929 Mw; Comp. A: 80% AA/20% EA, 21,000 Mw; Comp. B: 90% AA/10% EA, 18, 929 Mw;Comp. C: 80% AA/20% EA, 25,372 Mw; Comp. D: 90% AA/10% EA, 27,935 Mw.

Experiment 581

32.3% surfactant/soap formulation with rheology modifier for formulation stability testing.

The pH of the formulation was adjusted to 8.5 with 10% NaOH.

Formulation stability test of 32.3% surfactant plus fat soap formulation with 1% polymer solids. The final formulation pH was 8.5.

Note: The initial observations show that Sample 1 and Samples 3 through 12 are clearer and more stable than the experimental 0579 and 0580. Sample 2 and samples 13 to 16 were very turbid.

Stability data after 2 weeks under the conditions disclosed in the table

Stability: A single clear phase was observed with no precipitation or unevenness

Phase separation: A second liquid layer was observed at the bottom of the vessel indicating some phase incompatibility between the components.

Stability data after 4 weeks under the conditions disclosed in the table

Stability: A single clear phase was observed with no precipitation or unevenness

Phase separation: A second liquid layer was observed at the bottom of the vessel indicating some phase incompatibility between the components.

Sample index:

B: 28.3% EA/28.3% BA/43.3% MAA with 2% nDDM, 35,152 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA, With 2% nDDM, 31,771 Mw.

E: 28.3% EA/28.3% BA/43.3% MAA with 1.25% nDDM, 54,472 Mw; F: 50% EA/50% MAA with 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA, With 1.3% nDDM, 56,101 Mw.

H: 40% EA/50% MAA/10% LMA with 2% nDDM, 103,790 Mw; I: 50% EA/50% MAA with 3.0% nDDM, 24,506 Mw; J: 65% EA/35% MAA, With 3.0% nDDM, 22,897 Mw; K: 28.3% EA/28.3% BA/43.3% MAA with 3% nDDM, 21,929 Mw; Comp. A: 80% AA/20% EA, 21,000 Mw; Comp. B: 90 % AA/10% EA, 18,929 Mw; Comp. C: 80% AA/20% EA, 25,372 Mw; Comp. D: 90% AA/10% EA, 27,935 Mw.

Experiment 588

Total whiteness index after 2 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 10.5% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 12 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton wool (all from the test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Note: The following results were obtained from the Hunter Laboratory Colorimeter.

Sample composition:

B: 28.3% EA/28.3% BA/43.3% MAA with 2% nDDM, 35,152 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA, With 2% nDDM, 31,771 Mw; H: 40% EA/50% MAA/10% LMA with 2% nDDM, 103,790 Mw.

Experiment 589

Starting laundry conditions: The total volume of water is 1 L. Add 1.0 g of 10.5% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American test company's scale meter, 12 minutes wash, 3 minutes rinse (cold tap water), drum drying, two pieces 8.9 × 11.4 cm cotton, two pieces 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

E: 28.3% EA/28.3% BA/43.3% MAA with 1.25% nDDM, 54,472 Mw; F: 52.2% EA/47.8% MAA with 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA, 1.3% nDDM, 56,101 Mw; A: 45% EA/10% MA-23/45% MAA/, with 1% nDDM, 65,873 Mw.

Experiment 590B

Whiteness Index - WIE 313 (average of 4 values from the Hunter Laboratory Colorimeter) for a total of 10 cycles.

Starting laundry conditions: The total volume of water is 1L. Add 1.0g of 26.0% surfactant (1.0g / L), add 1.0g of 1% active polymer solution (10ppm concentration), 20 ° C washing conditions, the total hardness of water is 300ppm (2 / 1, Ca ^{+ 2} /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, two pieces 8.9 x 11.4 cm polyester and two 8.9 x 11.4 cm cotton wool (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Sample composition:

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; E: 28.3% EA/28.3% BA/43.3% MAA with 1.25% nDDM, 54,472 Mw; F: 52.2% EA/47.8% MAA, 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA with 1.3% nDDM, 56,101 Mw.

Experiment 592

Whiteness index after a total of 8 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 26.0% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton wool (all from the test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Sample composition:

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; O: 52.2% EA/47.8% MAA with 3.0% nDDM, 24,506 Mw; J: 65% EA/35% MAA with 3.0% nDDM , 22,897 Mw.

K: 28.3% EA/28.3% BA/43.3% MAA with 3.0% nDDM, 21,929 Mw.

Experiment 598

Starting laundry conditions:

The total volume of water is 1L. Add 1.0 g of 10.5% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American test company's scale meter, 12 minutes wash, 3 minutes rinse (cold tap water), drum drying, two pieces 8.9 × 11.4 cm cotton, two pieces 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; Q: 26.1% EA/26.1% BA/47.8% MAA, Comprising E: 52.2% BA/47.8% MAA with 2% nDDM, 31,852 Mw.

Experiment 599

Whiteness Index - WIE 313 (average of 4 values from the Hunter Laboratory Colorimeter) for a total of 10 cycles.

Starting laundry conditions: The total volume of water is 1L. Add 1.0 g of 26.0% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca ^{+ 2} /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, two Block 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Sample composition:

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; Q: 26.1% EA/26.1% BA/47.8% MAA, Comprising E: 52.2% BA/47.8% MAA with 2% nDDM, 31,852 Mw.

Experiment 604

Whiteness Index - WIE 313 (average of 4 values from the Hunter Laboratory Colorimeter) for a total of 10 cycles.

Starting laundry conditions:

The total volume of water is 1L. Add 1.0g of 26.0% surfactant (1.0g / L), add 1.0g of 1% active polymer solution (10ppm concentration), 20 ° C washing conditions, the total hardness of water is 300ppm (2 / 1, Ca ^{+ 2} /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, two pieces 8.9 x 11.4 cm polyester and two 8.9 x 11.4 cm cotton wool (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Sample composition:

F: 52.2% EA/47.8% MAA with 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA with 1.3% nDDM, 56,101 Mw; R: 26.1% EA/26.1% BA/47.8% MAA, With 1.25% nDDM, 56,281 Mw; Comp. F: 52.2% BA/47.8% MAA with 1.25% nDDM, 53,286 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 605

Starting laundry conditions:

The total volume of water is 1L. Add 1.0g of 35.6% surfactant (1.0 g / L), add 1.0g of 1% active polymer solution (10ppm concentration), 20 ° C washing conditions, the total hardness of water is 300ppm (2 / 1, Ca ^{+ 2} /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, two pieces 8.9 x 11.4 cm polyester and two 8.9 x 11.4 cm cotton wool (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

F: 52.2% EA/47.8% MAA with 1.5% nDDM, 51,080 Mw; G: 65% EA/35% MAA with 1.3% nDDM, 56,101 Mw; R: 26.1% EA/26.1% BA/47.8% MAA, With 1.25% nDDM, 56,281 Mw; Comp. E: 52.2% BA/47.8% MAA with 1.25% nDDM, 53,286 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 606

Starting laundry conditions:

The total volume of water is 1L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca ^{+ 2} /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4cm cotton, two pieces 8.9 × 11.4cm PE / cotton, two Block 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

0: 52.2% EA/47.8% MAA with 3.0% nDDM, 24,506 Mw; C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; F: 52.2% EA/47.8% MAA with 1.5% nDDM , 51,080 Mw; U: 52.2% EA/47.8% MAA with 0.5 nDDM, 161,160 Mw; T: 52.2% EA/47.8% MAA, no nDDM, 1,914,900 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 607

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

J: 65% EA/35% MAA with 3.0% nDDM, 22,897 Mw; D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; G: 65% EA/35% MAA with 1.3% nDDM , 56, 101 Mw; P: 65% EA/35% MAA with 0.5% nDDM, 226,770 Mw; L: 65% EA/35% MAA, no nDDM, 2,702, 200 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 608

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 1.0 g of 1% active polymer solution (10 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 2 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; N: 65% EA/20% MAA/15% AA with 2% nDDM, 39,995 Mw; M: 45% EA/35% MAA/ 20% MA with 2% nDDM, 37,808 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 609

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L) and add 1.0 g of 1% active polymer (5 ppm, 10 ppm, and 20 ppm concentration) of variable polymer (0.5 g, 1.0 g, and 2.0 g), 20 ° C washing conditions, total water hardness of 300 ppm (2 / 1, Ca ^{+ 2} / Mg ^{+ 2} ), American testing company's scale meter, 60 minutes wash, 3 minutes rinse (cold tap water), The drum was dry, two pieces of 8.9 x 11.4 cm cotton, two pieces of 8.9 x 11.4 cm PE/cotton, two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition: D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 610

Starting laundry conditions:

The total volume of water is 1L. Add 1.0g of 35.6% surfactant (1.0 g/L) and add variable (0.5g, 1.0g, and 2.0g) of 1% active polymer (5 ppm, 10 ppm, and 20 ppm concentration) Change polymer, 20 ° C washing conditions, water total hardness of 300 ppm (2 / 1, Ca ^{+ 2} / Mg ^{+ 2} ), American test company's scale meter, 60 minutes wash, 3 minutes rinse (cold tap water), The drum was dry, two pieces of 8.9 x 11.4 cm cotton, two pieces of 8.9 x 11.4 cm PE/cotton, two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton wool (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition: C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 612

Starting laundry conditions:

The total volume of water is 1L. Add 1.0 g of 35.6% surfactant (1.0 g/L) and add variable (0.5g, 1.0g, and 2.0g) of 1% active polymer (5ppm, 10ppm, and 20ppm concentration) of polymer, 20 °C washing conditions, the total hardness of water is 300ppm (2/1, Ca ⁺² /Mg ⁺² ), the American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two 8.9 x 11.4 cm cotton, two pieces 8.9 x 11.4 cm PE/cotton, two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton wool (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

S: 58.6% EA/41.4% MAA with 2% nDDM, 31,610 Mw.

35.6% surfactant preparation with rheology modifier (ACUSOL 820)

Experiment 613

Starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.6% surfactant (1.0 g/L), add 3.0 g of 1% active polymer solution (30 ppm concentration), and wash at 20 °C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Total whiteness index after 9 cycles - WIE313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; N: 65% EA/20% MAA/15% AA, With 2% nDDM, 39,995 Mw.

S: 58.6% EA/41.4% MAA with 2% nDDM, 31,610 Mw.

Experiment 614

Formulation stability test with 25.1% surfactant preparation of 1% and 3% polymer solids. The final formulation pH was 8.8.

25.1% surfactant preparation for formulation stability test with 1% active polymer

The pH of the formulation was adjusted to 8.8 with 10% NaOH.

25.1% surfactant preparation for formulation stability test with 3% active polymer

The pH of the formulation was adjusted to 8.8 with 10% NaOH.

1 week preparation stability results

4 weeks preparation stability results

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; N: 65% EA/20% MAA/15% AA, With 2% nDDM, 39,995 Mw.

S: 58.6% EA/41.4% MAA with 2% nDDM, 31,610 Mw; M: 45% EA/35% MAA/20% MA with 2% nDDM, 37,808 Mw; 0: 52.2% EA/47.8% MAA, With 3% nDDM, 24,096 Mw.

Q: 26.1% EA/26.1% BA/47.8% MAA with 2% nDDM, 33,422 Mw.

T: 52.2% BA/47.8% MAA with 2% nDDM, 31,852 Mw.

Experiment 615

Formulation stability test with 35.5% surfactant/fatty acid soap formulation with 1% and 3% polymer solids. The final formulation pH was 8.8.

Formulation for 35.5% surfactant preparation with 1% active polymer

Formulation for 35.5% surfactant preparation with 3% active polymer

1 week preparation stability results

4 weeks preparation stability results

C: 52.2% EA/47.8% MAA with 2% nDDM, 33,360 Mw; D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; N: 65% EA/20% MAA/15% AA, With 2% nDDM, 39,995 Mw; S: 58.6% EA/41.4% MAA with 2% nDDM, 31,610 Mw; M: 45% EA/35% MAA/20% MA with 2% nDDM, 37,808 Mw; 52.2% EA/47.8% MAA with 3% nDDM, 24,096 Mw; Q: 26.1% EA/26.1% BA/47.8% MAA with 2% nDDM, 33,422 Mw.

T: 52.2% BA/47.8% MAA with 2% nDDM, 31,852 Mw.

Experiment 623

Formulation stability test of 45.03% surfactant preparation with 4.18% active polymer solids. The final formulation pH was 8.8.

1 week and 3 weeks formulation stability results

Experiment 625

35.0% surfactant preparation with rheology modifier (ACUSOL 820) starting laundry conditions:

The total volume of water is 1L. Add 1.0g of 35.0% surfactant (1.0 g / L), add 1g of 1% active polymer solution (10ppm concentration), 20 ° C washing conditions, the total hardness of water is 300 ppm (2 / 1, Ca ^{+ 2} /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces 8.9 × 11.4 cm cotton, two pieces 8.9 × 11.4cm PE / cotton, two 8.9 x 11.4 cm polyester and two 8.9 x 11.4 cm cotton wool (all from test fabric). At the beginning of each wash, 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of a 25% large oak clay slurry were added. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; V: 75% EA/25% MAA with 2% nDDM, 37, 403 Mw; W: 58% EA/15% AA/27% MAA, With 2% nDDM, 37,878 Mw.

X: 40% EA/60% MAA with 2% nDDM, 52,545 Mw.

Experiment 626

35.0% surfactant preparation with rheology modifier (ACUSOL 820) starting laundry conditions:

The total volume of water is 1 L. Add 1.0 g of 35.0% surfactant (1.0 g/L), add 1 g of 1% active polymer solution (10 ppm concentration), and wash at 20 ° C. The total hardness of water is 300 ppm (2/1, Ca). ⁺² /Mg ⁺² ), American testing company's scale meter, 60 minutes washing, 3 minutes washing (cold tap water), drum drying, two pieces of 8.9 × 11.4 cm cotton, two pieces of 8.9 × 11.4 cm PE / cotton, Two pieces of 8.9 x 11.4 cm polyester and two pieces of 8.9 x 11.4 cm cotton (all from test fabric). At the beginning of each wash, add 2.5 g of dusty lotion (a gift from Science Service) and 2.5 g of 25% large oak clay slurry. Prior to the experiment, all fabrics were washed 3X in a PUREX FREE CLEAR detergent base.

Whiteness index after a total of 3 cycles - WIE 313 (average of 4 values from Hunter's laboratory colorimeter):

Sample composition:

D: 65% EA/35% MAA with 2% nDDM, 31,771 Mw; Comp. C: 80% AA/20% EA, 25,372 Mw; W: 58% EA/15% AA/27% MAA with 2% nDDM, 37, 878 Mw.

Y: 75% EA/25% AA with 2% nDDM, 41,450 Mw.

Claims (10)

A laundry detergent composition comprising: (a) 8 to 50% by weight of a surfactant; (b) 0.05 to 4% by weight of at least one polymer having a _Mw of 15,000 to 170,000 comprising the following polymeric residues: i) 40 to 80% by weight of a C ₁ -C ₄ alkyl acrylate wherein at least 4/10 by weight of the C ₁ -C ₄ alkyl acrylate is ethyl acrylate; (ii) 20 to 52% by weight of C ₃ -C _{a 6} carboxylic acid monomer; and (iii) 0 to 10% by weight of a monomer having an alkyl group having at least 10 carbon atoms; and (c) 35 to 85% by weight of water; wherein the at least one polymer is not Cationic modified polymer. The laundry detergent composition of claim 1, wherein the polymer comprises the following polymeric residues: (i) 45 to 78 wt% of a C ₁ -C ₄ alkyl acrylate; (ii) 22 to 52 wt% of a (meth)acrylic monomer; and (iii) 0 to 8 wt% of a monomer having an alkyl group having at least 10 carbon atoms. The laundry detergent composition of claim 2, wherein the C ₁ -C ₄ alkyl acrylate is at least 6/10 ethyl acrylate. A laundry detergent composition as claimed in claim 3, which comprises from 0.3 to 3.5% by weight of the polymer. The laundry detergent composition of claim 4, wherein the polymer comprises the following polymeric residues: (i) 50 to 78% by weight of a C ₁ -C ₄ alkyl acrylate; (ii) 22 to 50% by weight of a (meth)acrylic monomer; and (iii) 0 to 6% by weight of a polymerized residue of a monomer having an alkyl group having at least 10 carbon atoms. The scope of the patent application of paragraph 5, wherein the laundry detergent composition, wherein the acrylic acid ester of C ₁ -C ₄ alkyl acrylate is at least 8/10 system. The laundry detergent composition of claim 6, wherein the polymer comprises at least 8 wt% of a polymerized residue of acrylic acid. The laundry detergent composition of claim 7, wherein the polymer comprises no more than 3% by weight of a polymerized residue of a monomer having an alkyl group having at least 6 carbon atoms. The laundry detergent composition of claim 8, wherein the polymer comprises at least 10% by weight of a polymerized residue of acrylic acid. The laundry detergent composition of claim 2, wherein the at least one polymer has a _{Mw of} 20,000 to 60,000.